Diphenyl ether derivatives and herbicides containing same

ABSTRACT

Novel diphenyl ether hydrazine derivatives, particularly 2-nitro-5 (nucleus-substituted phenoxy) phenylhydrazine derivatives are provided. They are useful as a selective herbicide having a high herbicidal acitivity and residual efficacy.

This application is a continuation application of Ser. No. 91,858, filedNov. 6, 1979, abandoned.

BACKGROUND OF THE INVENTION

The present invention relates to novel diphenyl ether compounds andnovel herbicides containing at least one of the compounds as an activeingredient.

A number of diphenyl ether compounds have heretofore been studied fortheir practical use as herbicides, but these compounds are, in manycases, much different in the herbicidal activity, the developing manner,the selectivity, the durability of efficacy, etc., depending on slightdifferences in the chemical structures such as the kind, number andposition of their substituents, and it is very difficult to anticipatethe herbicidal activity of compounds from the similarity of the chemicalstructures of compounds.

As disclosed in e.g. U.S. Pat. No. 3,316,080 and Japanese PatentPublication No. 9898/1963, it is well-known that some of diphenyl ethercompounds have superior herbicidal activities. For example,2,4,6-trichloro-4'-nitrodiphenyl ether and2,4-dichloro-3'-methoxy-4'-nitrodiphenyl ether have been broadly used asherbicides for initial period paddy field.

However, since these compounds are insufficient in the residual efficacyand inconvenient in that it is difficult to completely control weedswhen their use time is missed, it has been desired to develop herbicidesfor paddy field, having a higher herbicidal activity and a saferselectivity than those of the above-mentioned known diphenyl ethercompounds, and also a herbicidal activity capable of controllingperennial weeds of paddy field which are difficult to control.

On the other hand, 2,4-dichloro-4'-nitrodiphenyl ether has been broadlyused as a herbicide for dry field crops, and besides, certain diphenylether compounds have been known, but since these compounds areinsufficient in the efficacy against broad-leaved weeds, it has beenalso desired to develop herbicides for dry field crops, having a higherherbicidal activity and a safer selectivity than those of these knowndiphenyl ether compounds.

SUMMARY OF THE INVENTION

An object of the present invention is to provide novel diphenyl etherderivatives having a superior herbicidal activity.

Another object of the present invention is to provide novel herbicideshaving a high selectivity and residual efficacy and capable ofcontrolling even perennial weeds which are difficult to control.

In accordance with the present invention, there are provided noveldiphenyl ether compounds expressed by the following general formula Iand herbicides containing at least one of them as an active ingredient:##STR1## wherein

(1) A and B each represent a halogen atom, a lower alkyl group or ahalogen-substituted lower alkyl group;

(2) m and n each represent an integer of 0˜3, and m+n=0˜3; and

(3) R represents ##STR2## (this group being a group having a cyclicgroup containing one nitrogen atom therein), ##STR3## (in the case ofthis group, the general formula I constitutes two molecules bonded byY), wherein

(a) R¹ represents hydrogen atom, an alkyl group, preferably a loweralkyl group, a lower alkenyl group, an alkynyl group, an unsubstitutedphenyl group, a substituted phenyl group, preferably ahalogen-substituted phenyl group, an alkoxycarbonyl group, preferably alower alkoxycarbonyl group, an unsubstituted phenoxycarbonyl group, asubstituted phenoxycarbonyl group, preferably a halogen-substitutedphenoxycarbonyl group, an alkylcarbamoyl group, preferably a loweralkylcarbamoyl group, an alkyl (thiocarbamoyl) group, an unsubstitutedbenzoyl group, a substituted benzoyl group, preferably ahalogen-substituted benzoyl group, an unsubstituted acyl group or ahalogen-substituted acyl group;

(b) R² and R³ each represent hydrogen atom, an alkyl group, preferably alower alkyl group, a lower alkenyl group, a cycloalkyl group, anunsubstituted phenyl group, an O,O-dialkylthiophosphoryl group, ##STR4##wherein

(i) R⁶ and R⁷ each represent hydrogen atom or a lower alkyl group;

(ii) R⁸ represents hydrogen atom, an alkyl group, preferably a loweralkyl group, a lower alkenyl group, unsubstituted phenyl group, asubstituted phenyl group, preferably a halogen-substituted phenyl group,benzyl group, a halogen-substituted lower alkyl group, asubstituted-phenoxy, substituted lower alkyl group, an unsubstitutedphenoxy, substituted lower alkyl group, a lower alkoxy-substituted loweralkyl group, a carboxy-substituted alkyl group, preferably acarboxy-substituted lower alkyl group, a lower alkoxycarbonyl group, analkoxycarbonyl-substituted alkyl group, preferably analkoxycarbonyl-substituted lower alkyl group, a carboxy-substitutedlower alkenyl group, an alkoxycarbonyl-substituted lower alkenyl group,acetyl group, an alkylthio group, phenoxy group or a lower alkoxy group;

(iii) R⁹ represents a lower alkyl group, unsubstituted phenyl group, asubstituted phenyl group, preferably a lower alkyl-substituted phenylgroup or an alkylamino group, preferably a lower alkylamino group;

(iv) X represents oxygen atom or sulfur atom;

(v) R¹⁰ represents hydrogen atom, an alkyl group, a lower alkenyl group,a cycloalkyl group, unsubstituted phenyl group or a substituted phenylgroup, preferably a halogen-substituted phenyl group; and ##STR5##wherein n' represents an integer of 2-5;

(c) R⁴ and R⁵ each represent hydrogen atom, a halogen atom, an alkylgroup, a lower alkenyl group, unsubstituted phenyl group, a styrylgroup, a lower alkoxy group, a halogen-substituted lower alkyl group, ahydroxy-substituted lower alkyl group, a cyano-substituted lower alkylgroup, a carboxy-substituted lower alkyl group, a loweralkoxycarbonyl-substituted lower alkyl group, a lower alkylthio group, afuryl group or R⁴ and R⁵ together form an alkylene group; and

(d) Y represents ##STR6## wherein n" represents an integer of 1-4.

DETAILED DESCRIPTION OF THE INVENTION

Examples of the compounds of the present invention represented by theabove-mentioned general formula I are illustrated in Table 1 and morespecifically in Table 2.

                                      TABLE 1                                     __________________________________________________________________________     ##STR7##            X.sub.n = H, 3-Cl, 4-Cl, 2,4-Cl.sub.2, 3,4-Cl.sub.2                           2,4,6-Cl.sub.3, 2,4-Cl.sub.2 6F, 4-CH.sub.3,                                  3,5-(CH.sub.3).sub.2, 2CH.sub.3 4Cl, 2Cl4CF.sub.3,                            2Cl4CCl.sub.3.                                            ##STR8##                                                                                           ##STR9##                                                                      ##STR10##                                                                     ##STR11##                                                                     ##STR12##                                                                     ##STR13##                                                                     ##STR14##                                                                     ##STR15##                                                ##STR16##           R = NHNH.sub.2, NHNHCH.sub.3, NHNHCH.sub.2 CHCH.sub.2                         ,                                                                              ##STR17##                                                                     ##STR18##                                                                     ##STR19##                                                                     ##STR20##                                                                     ##STR21##                                                                     ##STR22##                                                                     ##STR23##                                                                     ##STR24##                                                                     ##STR25##                                                ##STR26##                                                                                          ##STR27##                                                                     ##STR28##                                                                     ##STR29##                                                                     ##STR30##                                                                     ##STR31##                                                                     ##STR32##                                                                     ##STR33##                                                ##STR34##                                                                                          ##STR35##                                                                     ##STR36##                                                                     ##STR37##                                                ##STR38##                                                                                          ##STR39##                                                ##STR40##                                                                                          ##STR41##                                                                     ##STR42##                                                ##STR43##                                                                                          ##STR44##                                               __________________________________________________________________________

The novel diphenyl ether compounds of the present invention are superiorin controlling weeds of paddy field. They can be used for either thetreatment of filled-water prior to occurrence of weeds or the treatmentduring the growth period in the paddy field where transplantation hasbeen carried out. The compounds of the present invention exhibit asuperior herbicidal activity against Smallerflower umbrellaplant,Scirpus juncoides and Eleocharis kuroguwai, belonging to Cyperaceae, notto mention Barnyardgrass which is a seriously harmful weed in paddyfield, Narrowleaf waterplantain and Sagittaria trifolia belonging toAlismataceae, Monochria vaginalis, Rotala indica, Ludwigia prostrata andEclipta prostrata which are annual broad-leaf weeds, etc., and have ahigh selectivity that the phytotoxicity upon transplanted aquatic riceis very small.

Further, the compounds have much superior specific features that theyexhibit a superior herbicidal activity and residual efficacy in the soiltreatment prior to occurrence of weeds and the treatment of stems andleaves as well as soil, against weeds which raise problems in the dryfield crops, such as Crabgrass, Foxtail, Barnyardgrass, Bluegrass,Foxtailgrass, Johnsongrass, Bermudagrass, Quackgrass, Redroot pigweed,Lambsquarters, Smartweed, Velvet leaf, Morningglory, Hertleaf cocklebur,Rumex japonicus, Wild mustard, Shepherdspurse, etc., and also have nophytotoxicity upon soybean and peanut belonging to Leguminosae, cotton,corn, wheat, etc., and further, have only a slight phytotoxicity even inthe treatment in a higher concentration.

The novel compounds represented by the general formula I may beprepared, for example, according to the following reaction, startingfrom compounds of formula II which are known and may be prepared, forexample, by the processes disclosed in Japanese Patent Kokai No. 49-236,No. 50-37740 and 54-95527. ##STR45## wherein X' stands for a halogenatom, nitro group or a phenoxy group represented by the formula,##STR46## R₁, R₂ and R₃ each stand for hydrogen or a lower alkyl group,and (A)_(m) and (B)_(n) are as defined in the general formula I.

When the compound of the general formula II is dissolved in a suitableorganic solvent, e.g. benzene, dioxane or dimethylformamide andalkylhydrazine of the general formula III is added, reaction is easilycarried out so that the compounds of the general formula I' can beobtained with a high yield.

Using the compounds of the formula I' which are of course included inthe present invention, various compounds of the formula I can beprepared by per se known processes as illustrated hereunder: ##STR47##R₁˜2 =H or lower alkyl R₃ =H ##STR48## R₁ =H or lower alkyl R₂˜3 =H##STR49## R₁ =H or lower alkyl R₂˜3 =H ##STR50## R₁ =H or lower alkylR₂˜3 =H ##STR51## R₁ =H or lower alkyl R₂˜3 =H ##STR52## R₁˜2 =H orlower alkyl R₃ =H ##STR53## X=O, S R₁˜2 =H or lower alkyl

R₃ =H ##STR54## R₁˜2 =H or lower alkyl R₃ =H ##STR55## R₁˜2 =H or loweralk. R₃ =H ##STR56## R₁˜2 =H or low. alk. R₃ =H ##STR57## R₁˜2 =H orlow. alk. R₃ =H ##STR58## R₁ =H or low. alk. R₂ =H ##STR59## R₁˜2 =H orlow. alk. R₃ =H ##STR60## R₁˜2 =H or low. alk. R₃ =H

Herbicidal activity compounds of the formula I may be prepared accordingto the following reactions, starting from other derivatives than thecompounds of the formula I':

Next, the preparation of the compounds of the general formula I will beillustrated in more detail, by way of the following Examples at thebeginning of which the compound number set forth in Table 2 isindicated.

EXAMPLE 1 Preparation of2-chloro-4-trifluoromethyl-3'-hydrazino-4'-nitrodiphenyl ether (compoundNo. 19)

2-Chloro-4-trifluoromethyl-3',4'-dinitrodiphenyl ether (7.2 g) anddioxane (50 ml) were introduced into a 100 ml four-neck flask, and afterdissolution, hydrazine hydrate (2 g) was dropwise added at 5°-10° C.,followed by stirring at 25°-30° C. for 2 hours. After completion of thereaction, the reaction liquid was discharged into 200 ml of water, andthe resulting precipitated crystal was collected by filtration, washedwith water and dried. The crystal thus obtained was recrystallized fromethanol to obtain 5 g of an objective product having a melting point of131.5°-132° C.

EXAMPLE 2 Preparation of 2,4-dichloro-3'-hydrazino-4'-nitrodiphenylether (compound No. 7)

2,4-Bis(2,4-dichlorophenoxy)nitrobenzene (44.5 g) and dioxane (100 ml)were introduced into a 200 ml four-neck flask, and after dissolution,hydrazine hydrate (15 ml) was added, followed by stirring at 60°-80° C.for 8 hours. The resulting liquid after completion of the reaction wasdischarged into water, and the resulting precipitated crystal wascollected by filtration, washed with water and dried. The crystal thusobtained was recrystallized from ethanol to obtain 26 g of an objectiveproduct having a melting point of 124°-125° C.

EXAMPLE 3 Preparation of3,5-dimethyl-3'-(2-acetylhydrazino)-4'-nitrodiphenyl ether (compound No.18)

3,5-Dimethylphenol (7 g), potassium carbonate (7.5 g) anddimethylformamide (100 ml) were introduced into a 200 ml four-neckflask, and 2-acetyl-1-(5-chloro-2-nitrophenyl)hydrazine (11 g) wasadded, followed by stirring at 140°-145° C. for 5 hours. The resultingliquid after completion of the reaction was discharged into water andextracted with a solvent mixture of benzene/ethyl acetate, followed bywashing with water and drying on anhydrous sodium sulfate. After drying,the solvents were distilled off under reduced pressure, followed bypurification, by means of a silica gel column employing benzene/ethylacetate (1:1) as a developing solvent, to obtain 2 g of an objectiveproduct having a melting point of 192°-193° C.

EXAMPLE 4 Preparation of2,4-dichloro-3'-(ethoxymethylene)-hydrazino-4'-nitrodiphenyl ether(compound No. 10)

2,4-Dichloro-3'-hydrazino-4'-nitrodiphenyl ether (2 g) and benzene (50ml) were introduced into a 100 ml four-neck flask, and afterdissolution, ethyl orthoformate (1 ml) and conc. sulfuric acid (onedrop) were added, followed by stirring under reflux for 30 minutes. Theresulting reaction liquid was cooled, washed with water and dried onanhydrous sodium sulfate, followed by distilling off benzene underreduced pressure and recrystallization from ethanol, to obtain 2.1 g ofan objective product having a melting point of 135°-136° C.

EXAMPLE 5 Preparation of2-chloro-4-trifluoromethyl-3'-(2-n-butylhydrazino)-4'-nitrodiphenylether (compound No. 21) and2-chloro-4-trifluoromethyl-3'-(1-n-butylhydrazino)-4'-nitrodiphenylether (compound No. 98)

2-Chloro-4-trifluoromethyl-3',4'-dinitrodiphenyl ether (3.6 g) anddioxane (30 ml) were introduced into a 50 ml four-neck flask, and afterdissolution, n-butylhydrazine (2 g) was dropwise added, followed bystirring at room temperature for 4 hours. To the resulting reactionliquid was added about 200 ml of benzene, followed by washing withwater, and drying on anhydrous sodium sulfate. After distilling offbenzene under reduced pressure, purification and separation were carriedout by means of a silica gel column employing benzene as a developingsolvent to obtain liquids of2-chloro-4-trifluoromethyl-3'-(2-n-butylhydrazino)-4'-nitrodiphenylether (1.2 g) and2-chloro-4-trifluoromethyl-3'-(1-n-butylhydrazino)-4'-nitrodiphenylether (1.3 g).

EXAMPLE 6 Preparation of2-chloro-4-trifluoromethyl-3'-(2,2-dimethylhydrazino)-4'-nitrodiphenylether (compound No. 23)

2-Chloro-4-trifluoromethyl-3',4'-dinitrodiphenyl ether (7.2 g) anddioxane (100 ml) were introduced into a 200 ml four-neck flask, andafter dissolution, 1,1-dimethylhydrazine (2.7 g) was added at roomtemperature, followed by stirring at 50°-60° C. for 5 hours. Theresulting reaction liquid was cooled and then discharged into water,followed by extraction with benzene and drying on anhydrous sodiumsulfate. After distilling off benzene under reduced pressure,purification was carried out by means of a silica gel column employingbenzene as a developing solvent to obtain 7.7 g of a liquid as anobjective product.

EXAMPLE 7 Preparation of2-chloro-4-trifluoromethyl-3'-(2-ethoxycarbonylmethylhydrazino)-4'-nitrodiphenylether (compound No. 25)

2-Chloro-4-trifluoromethyl-3'-hydrazino-4'-nitrodiphenyl ether (3.5 g),triethylamine (1 g) and toluene (100 ml) were introduced into a 200 mlfour-neck flask, and after dissolution, ethyl bromoacetate (1.7 g) wasadded, followed by stirring under reflux for 10 hours. After thestirring, the resulting reaction material was discharged into water, andthe resulting toluene layer was washed with dilute hydrochloric acid andwater and dried on anhydrous sodium sulfate. Toluene was distilled offunder reduced pressure and the resulting oily substance was purified bymeans of a silica gel column employing benzene as a developing solventto obtain 1 g of an objective product having a melting point of 99°-100°C.

EXAMPLE 8 Preparation of2-chloro-4-trifluoromethyl-3'-(o,o-diethylthiophosphonylhydrazino)-4'-nitrodiphenylether (compound No. 26)

2-Chloro-4-trifluoromethyl-3'-hydrazino-4'-nitrodiphenyl ether (3.4 g),triethylamine (1.1 g) and isopropanol (100 ml) were introduced into a200 ml four-neck flask, and after dissolution, o,o-diethylthiophosphonylchloride (1.9 g) was dropwise added at room temperature, followed bystirring at 50°-60° C. for 4 hours. The resulting material was cooledand then discharged into water. The resulting oily substance wasextracted twice with 150 ml of benzene, followed by washing with dilutehydrochloric acid, sodium bicarbonate aqueous solution and water anddrying on anhydrous sodium sulfate. The solvent was distilled off underreduced pressure, to give 5 g of an oily substance, which was purifiedby means of a silica gel column employing benzene as a developingsolvent to obtain 4 g of an objective product having a melting point of70°-71° C.

EXAMPLE 9 Preparation of2-chloro-4-trifluoromethyl-3'-(2-formylhydrazino)-4'-nitrodiphenyl ether(compound No. 27)

2-Chloro-4-trifluoromethyl-3'-hydrazino-4'-nitrophenyl ether (3.4 g),formic acid (0.5 g) and ethanol (30 ml) were introduced into a 50 mlfour-neck flask, followed by dissolution and then stirring under refluxfor 2 hours. After cooling, ethanol was distilled off under reducedpressure. A solid substance thus obtained was recrystallized frombenzene/ethanol to obtain 1.6 g of an objective product having a meltingpoint of 176°-177° C.

EXAMPLE 10 Preparation of2-chloro-4-trifluoromethyl-3'-(2-crotonoylhydrazino)-4'-nitrodiphenylether (compound No. 33)

2-Chloro-4-trifluoromethyl-3'-hydrazino-4'-nitrodiphenyl ether (3.5 g)and glacial acetic acid (50 ml) were introduced into a 100 ml four-neckflask, and after dissolution, crotonic anhydride (2 g) was added at roomtemperature, followed by stirring at 80°-90° C. for 3 hours. Theresulting reaction liquid was discharged into 300 ml of water andextracted with ethyl acetate, followed by washing with water and thendrying on anhydrous sodium sulfate. The solvent was distilled off underreduced pressure, and the resulting material was recrystallized frombenzene/n-hexane to obtain 2.8 g of an objective product having amelting point of 170°-171° C.

EXAMPLE 11 Preparation of2-chloro-4-trifluoromethyl-3'-(2-chloroacetylhydrazino)-4'-nitrodiphenylether (compound No. 37)

2-Chloro-4-trifluoromethyl-3'-hydrazino-4'-nitrodiphenyl ether (3.5 g),triethylamine (1.2 g) and benzene (100 ml) were introduced into a 200 mlfour-neck flask, and after dissolution, chloroacetyl chloride (1.3 g)was dropwise added, followed by heating under reflux with stirring for 2hours. The resulting material was cooled and then discharged into water,followed by collecting the resulting crystal by filtration, washing withwater and drying. The resulting raw crystal was recrystallized frombenzene to obtain 2.9 g of an objective product having a melting pointof 188°-188.5° C.

EXAMPLE 12 Preparation of2-chloro-4-trifluoromethyl-3'-(3-ethoxycarbonylpropionyl)hydrazino-4'-nitrodiphenylether (compound No. 44)

2-Chloro-4-trifluoromethyl-3'-hydrazino-4'-nitrodiphenyl ether (2 g),pyridine (0.6 ml) and tetrahydrofuran (20 ml) were introduced into a 50ml four-neck flask, and after dissolution, acid chloride of monoethylsuccinate (1 g) was slowly added under cooling at -5°-0° C., followed bystirring at room temperature for one hour. The resulting reaction liquidwas discharged into water and extracted with benzene, followed by dryingon anhydrous sodium sulfate. Benzene was distilled off under reducedpressure and the resulting material was purified by means of a silicagel column employing benzene/ethyl acetate (4:1) as a developing solventto obtain 1 g of an objective product having a melting point of117°-118° C.

EXAMPLE 13 Preparation of2-chloro-4-trifluoromethyl-3'-(2-p-tosylhydrazino)-4'-nitrodiphenylether (compound No. 49)

2-Chloro-4-trifluoromethyl-3'-hydrazino-4'-nitrodiphenyl ether (3.4 g)and pyridine (30 ml) were introduced into a 100 ml four-neck flask, andp-toluenesulfonyl chloride (2 g) was added at room temperature, followedby stirring for one hour and allowing the resulting material to standover night. The resulting reaction liquid was discharged into water andextracted with benzene, followed by washing with water and drying onanhydrous sodium sulfate. After distilling off the solvent under reducedpressure, the resulting material was purified by means of a silica gelcolumn employing benzene/ethyl acetate (4:1) as a developing solvent toobtain 4 g of an objective product having a melting point of 146°-147°C.

EXAMPLE 14 Preparation of2-chloro-4-trifluoromethyl-3'-ethoxycarbonylhydrazino-4'-nitrodiphenylether (compound No. 53)

2-Chloro-4-trifluoromethyl-3'-hydrazino-4'-nitrodiphenyl ether (3.5 g),pyridine (0.9 g) and toluene (50 ml) were introduced into a 100 mlfour-neck flask, and after dissolution and subsequent cooling to 0°-5°C., ethyl chlorocarbonate (1.2 g) was slowly added, followed by stirringat the same temperature for one hour. Toluene was distilled off underreduced pressure from the resulting reaction liquid, and 100 ml of waterwas added, followed by collecting the resulting crystal by filtration. Araw crystal thus obtained was recrystallized from ethanol/water toobtain 2.9 g of an objective product having a melting point of 118°-119°C.

EXAMPLE 15 Preparation of2-chloro-4-trifluoromethyl-3'-(n-octylthio)carbonylhydrazino-4'-nitrodiphenylether (compound No. 58)

2-chloro-4-trifluoromethyl-3'-hydrazino-4'-nitrodiphenyl ether (3.5 g),triethylamine (1 g) and benzene (100 ml) were introduced into a 200 mlfour-neck flask, and after dissolution, n-octylthiocarbonyl chloride(2.1 g) was dropwise added at room temperature, followed by stirring at55°-60° C. for 3 hours. The resulting material was cooled and thendischarged into water, followed by separating the resulting benzenelayer, washing with water and drying on anhydrous sodium sulfate.Benzene was then distilled off, and the resulting material was purifiedby means of a silica gel column employing benzene as a developingsolvent to obtain 2.3 g of an objective product having a melting pointof 83°-84° C.

EXAMPLE 16 Preparation of2-chloro-4-trifluoromethyl-3'-(4-ethylsemicarbazido)-4'-nitrodiphenylether (compound No. 60)

2-Chloro-4-trifluoromethyl-3'-hydrazino-4'-nitrodiphenyl ether (3.4 g)and toluene (50 ml) were introduced into a 100 ml four-neck flask. Afterdissolution, ethyl isocyanate (1.4 g) dissolved in 20 ml of toluene and2-3 drops of dibutyltin laurate were dropwise added at room temperature,and temperature was slowly elevated, followed by stirring under refluxfor one hour. After cooling, the resulting precipitated crystal wascollected by filtration and washed with toluene to obtain 3.3 g of anobjective product having a melting point of 184°-185° C.

EXAMPLE 17 Preparation of2-chloro-4-trifluoromethyl-3'-thiosemicarbazido-4'-nitrodiphenyl ether(compound No. 65)

2-Chloro-3-trifluoromethyl-3'-hydrazino-4'-nitrodiphenyl ether (3.5 g),ethanol (50 ml), conc. hydrochloric acid (0.9 ml) and sodium thiocyanate(0.8 g) were introduced into a 100 ml four-neck flask, and agitatedunder reflux for 6 hours. Ethanol was then distilled off under reducedpressure, followed by adding 200 c.c. of water, collecting the resultingcrystal by filtration and recrystallization from ethanol/water to obtain0.9 g of an objective product having a melting point of 180.5°-183° C.

EXAMPLE 18 Preparation of2-chloro-4-trifluoromethyl-3'-(4-ethyl)thiosemicarbazido-4'-nitrodiphenylether (compound No. 67)

2-Chloro-4-trifluoromethyl-3'-hydrazino-4'-nitrodiphenyl ether (3.4 g)and toluene (100 ml) were introduced into a 200 ml four-neck flask, andafter dissolution, ethyl isothiocyanate (0.9 g) and dibutyltin laurate(2-3 drops) were dropwise added, followed by stirring under reflux for10 hours. After cooling, toluene was distilled off under reducedpressure to obtain 5 g of an oily substance containing a crystal, towhich a small amount of benzene was added. The resulting crystal wascollected by filtration to obtain 1.7 g of an objective product having amelting point of 180°-181° C.

EXAMPLE 19 Preparation of2-chloro-4-trifluoromethyl-3'-(dichloromaleinimidoyl)amino-4'-nitrodiphenylether (compound No. 71)

2-Chloro-4-trifluoromethyl-3'-hydrazino-4'-nitrodiphenyl ether (3.4 g),dichloromaleic anhydride (1.7 g) and acetic acid (100 ml) wereintroduced into a 200 ml four-neck flask, followed by stirring at 110°C. for 2 hours. After cooling, the resulting material was dischargedinto water, and precipitated crystal was collected by filtration,followed by washing with water and a small amount of ethanol to obtain3.3 g of an objective product having a melting point of 149°-150° C.

EXAMPLE 20 Preparation ofN-{5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrophenyl}amino-2,3-dihydroisoindolinone(compound No. 73)

2-Chloro-4-trifluoromethyl-3'-hydrazino-4'-nitrodiphenyl ether (3.5 g),triethylamine (2.2 g) and dioxane (100 ml) were introduced into a 200 mlfour-neck flask, and after dissolution, 2-chloromethylbenzoyl chloride(1.9 g) was added little by little at room temperature, followed bystirring at 95°-100° C. for 3 hours. After cooling, the resultingmaterial was discharged into water and extracted with benzene, followedby washing with an aqueous solution hydrogen sulfate and water anddrying with anhydrous sodium sulfate. After drying, benzene wasdistilled off under reduced pressure, and the resulting material waspurified by means of a silica gel column employing benzene/ethyl acetate(95:5) as a developing solvent to obtain 0.9 g of an objective producthaving a melting point of 207°-208° C.

EXAMPLE 21 Preparation of2-chloro-4-trifluoromethyl-3'-(1-methylhydrazino)-4'-nitrodiphenyl ether(compound No. 76)

2-Chloro-4-trifluoromethyl-3',4'-dinitrodiphenyl ether (36 g) anddioxane (300 ml) were introduced into a 500 ml four-neck flask, andmethylhydrazine (9 g) was dropwise added at 20° C. or lower, followed bystirring at room temperature for 2 hours. The resulting reaction liquidwas discharged into water and extracted with benzene, followed bywashing with water and drying on anhydrous sodium sulfate. Benzene wasdistilled off under reduced pressure and recrystallization from ethanolwas carried out to obtain 24 g of an objective product having a meltingpoint of 96°-97° C.

EXAMPLE 22 Preparation of2-chloro-4-trifluoromethyl-3'-(1-methyl-2-methylsulfonylhydrazino)-4'-nitrodiphenylether (compound No. 85) and2-chloro-4-trifluoromethyl-3'-{1-methyl-2,2-bis(methylsulfonyl)hydrazino}-4'-nitrodiphenylether (compound No. 86)

2-chloro-4-trifluoromethyl-3'-(1-methylhydrazino)-4'-nitrodiphenyl ether(3.6 g), triethylamine (1 g) and benzene (100 ml) were introduced into a200 ml four-neck flask, and methanesulfonyl chloride (1.7 g) wasdropwise added while temperature was maintained at 15° C. or lower,followed by stirring at room temperature for one hour. The resultingreaction liquid was discharged into water, and the resulting benzenelayer was washed with water and dried on anhydrous sodium sulfate. Afterdrying, benzene was distilled off under reduced pressure, and theresulting liquid was purified by means of a silica gel column employingbenzene/ethyl acetate (10:1) as a developing solvent to obtain 0.8 g of2-chloro-4-trifluoromethyl-3'-(1-methyl-2-methylsulfonylhydrazino)-4'-nitrodiphenylether having a melting point of 117°-118° C. and 2.5 g of2-chloro-4-trifluoromethyl-3'-{1-methyl-2,2-bis(methylsulfonyl)hydrazino}-4'-nitrodiphenylether having a melting point of 160°-161.5° C.

EXAMPLE 23 Preparation of2-chloro-4-trifluoromethyl-3'-{1-methyl-2-(N-methylsulfamoyl)hydrazino}-4'-nitrodiphenylether (compound No. 87)

2-Chloro-4-trifluoromethyl-3'-(1-methylhydrazino)-4'-nitrodiphenyl ether(3.6 g), triethylamine (1 g) and benzene (100 ml) were introduced into a200 ml four-neck flask, and methylaminosulfamoyl chloride (1.9 g) wasdropwise added at 15° C. or lower, followed by stirring at roomtemperature for one hour. The resulting material was discharged intowater, and the resulting benzene layer was twice washed with water andthen dried on anhydrous sodium sulfate. Benzene was distilled off underreduced pressure, followed by recrystallization from benzene/n-hexane(1:1) to obtain 3 g of an objective product having a melting point of124°-126° C.

EXAMPLE 24 Preparation of2-chloro-4-trifluoromethyl-3'-(1,2,2-triacetylhydrazino)-4'-nitrodiphenylether (compound No. 102)

2-Chloro-4-trifluoromethyl-3'-hydrazino-4'-nitrodiphenyl ether (3.5 g),triethylamine (1.2 g) and benzene (100 ml) were introduced into a 200 mlfour-neck flask, and after dissolution, acetyl chloride (2.6 g) wasdropwise added at 5°-10° C., followed by stirring at 40° C. for 2 hours.After cooling, the resulting material was discharged into water, and theresulting crystal was collected by filtration, followed by purificationby means of a silica gel column employing benzene/ethyl acetate (4:1) asa developing solvent to obtain 4 g of an objective product having amelting point of 106°-107° C.

EXAMPLE 25 Preparation of2-chloro-4-trifluoromethyl-3'-(2-acetyl-1-ethoxycarbonylhydrazino)-4'-nitrodiphenylether (compound No. 103)

2-Chloro-4-trifluoromethyl-3'-(2-acetylhydrazino)-4-nitrodiphenyl ether(3.9 g), triethylamine (1.2 g) and benzene (100 ml) were introduced intoa 200 ml four-neck flask, and after dissolution, ethyl chlorocarbonate(1.2 g) was dropwise added at 5°-10° C., followed by stirring at 40° C.for 2 hours. The resulting reaction liquid was discharged into water,and the resulting crystal was collected by filtration, followed bypurification by means of a silica gel column employing benzene/ethylacetate (4:1) as a developing solvent to obtain 1.5 g of an objectiveproduct having a melting point of 134°-135° C.

EXAMPLE 26 Preparation of2-chloro-4-trifluoromethyl-3'-(2-acetyl-1-ethylcarbamoylhydrazino)-4'-nitrodiphenylether (compound No. 104)

2-Chloro-4-trifluoromethyl-3'-(2-acetylhydrazino)-4'-nitrodiphenyl ether(3.9 g) and toluene (100 ml) were introduced into a 200 ml four-neckflask, and then a solution obtained by dissolving 0.8 g of ethylisocyanate in 5 ml of toluene and one drop of dibutyltin laurate wereadded at room temperature, followed by stirring under reflux for 6hours. Toluene was then distilled off under reduced pressure, followedby purification by means of a silica gel column employing benzene/ethylacetate (4:1) as a developing solvent to obtain 3.5 g of an oilysubstance as an objective product.

EXAMPLE 27 Preparation of2-chloro-4-trifluoromethyl-3'-(n-heptylidenehydrazino)-4'-nitrodiphenylether (compound No. 113)

2-Chloro-4-trifluoromethyl-3'-hydrazino-4'-nitrodiphenyl ether (3.5 g)and dioxane (30 ml) were introduced into a 50 ml four-neck flask, andafter dissolution, n-heptylaldehyde (1.5 g) and 3 drops of conc.hydrochloric acid were added at room temperature, followed by stirring 4hours. The resulting material was discharged into 200 ml of water,followed by collecting the resulting crystal by filtration andrecrystallization from ethanol to obtain 3.6 g of an objective producthaving a melting point of 93°-94° C.

EXAMPLE 28 Preparation of2-chloro-4-trifluoromethyl-3'-(1-chloroethylidene)hydrazino-4'-nitrodiphenylether (compound No. 123)

2-Chloro-4-trifluoromethyl-3'-(2-acetylhydrazino)-4'-nitrodiphenyl ether(4.5 g) and phosphorus pentachloride (2.9 g) were introduced into a 50ml four-neck flask, followed by stirring at 70° C. for about one houruntil no hydrogen chloride gas was evolved. After cooling, benzene wasadded, followed by extraction. The resulting benzene solution wasdecanted and used for the following reaction:

Phenol (3.2 g) and benzene (100 ml) were introduced into a 200 mlfour-neck flask, and the benzene solution prepared above was dropwiseadded while temperature was maintained at 10°-15° C., followed bystirring at 20° C. for 3 hours. Hydrogen chloride gas was removedemploying nitrogen gas, followed by distilling off benzene under reducedpressure to obtain 10 g of an oily substance, which was then purified bymeans of a silica gel column employing benzene as a developing solventto obtain 2.6 g of an objective product having a melting point of108°-113° C.

EXAMPLE 29 Preparation of2-chloro-4-trifluoromethyl-3'-(2-isopropylidenehydrazino)-4'-nitrodiphenylether (compound No. 124)

2-Chloro-4-trifluoromethyl-3'-hydrazino-4'-nitrodiphenyl ether (3.5 g)and acetone (50 ml) were introduced into a 100 ml four-neck flask, andafter dissolution, the resulting solution was allowed to stand at roomtemperature for one hour. Acetone was distilled off under reducedpressure from the reaction liquid to obtain 3.5 g of a raw crystal,which was recrystallized from ethanol to obtain 2.5 g of an objectiveproduct having a melting point of 134°-135° C.

EXAMPLE 30 Preparation of2-chloro-4-trifluoromethyl-3'-{bis(methylthio)methylene}hydrazino-4'-nitrodiphenylether (compound No. 140)

2-Chloro-4-trifluoromethyl-3'-hydrazino-4'-nitrodiphenyl ether (3.5 g)and ethanol (60 ml) were introduced into a 200 ml four-neck flask, andcarbon disulfide (2.3 g) was dropwise added with stirring. A solutionobtained by dissolving 1.2 g of potassium hydroxide in ethanol was thenadded, followed by stirring at room temperature for 30 minutes. Methyliodide (5 g) was further added, followed by stirring at 45°-50° C. forone hour. The resulting reaction liquid was discharged into water,followed by extraction with benzene and drying with anhydrous sodiumsulfate. Solvent was distilled off under reduced pressure, followed bypurification by means of a silica gel column employing benzene/n-hexane(1:1) as a developing solvent to obtain 0.5 g of an objective producthaving a melting point of 121°-124° C.

EXAMPLE 31 Preparation of oxalic acidbis[5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrophenyl]hydrazide(compound No. 171)

2-Chloro-4-trifluoromethyl-3'-hydrazino-4'-nitrodiphenyl ether (7.0 g),triethylamine (2.5 ml) and dioxane (80 ml) were introduced into a 200 mlfour-neck flask, and oxalic chloride (1.3 g) was dropwise added withstirring, followed by reaction at room temperature for 2 hours. Theresulting reaction liquid was discharged into water, and precipitatedcrystal was collected by filtration and air-dried. This crystal wasrecrystallized from a solvent mixture of dioxane/benzene to obtain 6.2 gof an objective product having a melting point of 266°-268° C.(decomposition).

EXAMPLE 32 Preparation of2-chloro-4-trifluoromethyl-3'-(2-methyl-2-acetylhydrazino)-4'-nitrodiphenylether (compound No. 173)

2-Chloro-4-trifluoromethyl-3'-(2-acetylhydrazino)-4'-nitrodiphenyl ether(7.8 g), anhydrous potassium carbonate (2.8 g) and ethanol (100 ml) wereintroduced into a 200 ml four-neck flask and heated. While the resultingliquid was agitated under reflux, methyl iodide (2.9 g) was added andreaction was carried out for 4 hours. The resulting reaction liquid wasdischarged into water, and precipitated crystal was collected byfiltration, and then recrystallized from methanol to obtain 4.9 g of anobjective product having a melting point of 101.5°-102.5° C.

Other compounds included in the above-mentioned general formula I can bealso synthesized according to any one of the above-mentioned methods,and the details of the synthesis method therefor will be shown in theitem "Synthesis method example No." of the following Table 2.

Next, representative compounds among those of the present inventionexpressed by the general formula I and their physical properties areillustrated in the following Table 2.

    TABLE 2      Substituents in  general formula I       No.poundCom-      ##STR62##      R example No.methodSynthesis cm.sup.-1)absorption spectra,(Infrared     rayMelting point (°C.) CHNClFSupper row, observed value;lower     row, calculated valueElemental analysis value %                  1      ##STR63##      NHNH.sub.2 1 95-97 51.6651.53 3.783.60 14.8815.02 12.2412.68 -- --  2 "      ##STR64##      10 151.5-153 52.2652.26 3.853.76 12.9913.06 10.9611.02 -- --  3 "      ##STR65##      29 105-106 56.3856.34 4.564.41 13.0813.14 11.1111.09 -- --  4 "      ##STR66##      29      ##STR67##      64.0163.95 7.137.00 9.689.73 8.538.21 -- --      5 "     ##STR68##      27 153-155 54.2154.04 4.364.27 11.0211.12 9.579.39 -- --      6 "     ##STR69##      30 111-112 46.8946.93 3.773.68 10.8510.95 9.339.24 -- 16.58      7     ##STR70##      NHNH.sub. 2 2 124-125 45.9145.88 3.022.89 13.5213.38 22.9422.57 -- --     8 "      ##STR71##      10 162-163 47.5547.21 3.833.11 12.0111.80 19.5219.91 -- --  9 "      ##STR72##      10 166-168 48.0948.67 3.263.54 11.1911.35 19.3419.16 -- --  10 "     NHNCHOC.sub.2 H.sub.5 4 135-136 49.00 3.66 11.93 18.99 -- --      48.67     3.54 11.35 19.16      11     ##STR73##      NHNH.sub.2 1 170-171 40.9841.37 2.382.31 12.5112.05 30.5330.05 -- --     12 "      ##STR74##      10 218-219 43.2743.05 2.972.58 10.7710.76  27.8127.23 -- --  13 "      ##STR75##      29 169-170 46.2046.35 3.093.11 11.0510.81 27.4827.37 -- --  14 "      ##STR76##      4 119-126 47.3447.19 3.603.73 9.189.71 24.9024.58 -- --      15     ##STR77##      NHNH.sub.2 1 148.5-149.5 43.3743.39 2.872.43 12.4712.65 21.6921.35     5.575.72 --  16 " NHNCHCH.sub.3 27 178-179 46.36 3.26 11.47 20.34 5.19     --      46.95 2.81 11.73 19.80 5.31      17 "     ##STR78##      29 146-148 48.2148.40 3.443.25 11.2811.29 19.1119.05 5.02 5.11 --  18      ##STR79##      ##STR80##      3 192-193 60.8760.85 5.635.43 12.9713.30 -- -- --      19     ##STR81##      NHNH.sub.2 1 131.5-132 44.5644.91 3.042.61 11.5612.08 10.3910.20     16.1116.59 --      20     ##STR82##      ##STR83##      3 133-135 59.3358.53 4.144.56 14.9814.63 -- -- --      21     ##STR84##      NHNHC.sub.4 H.sub.9      (n) 5     ##STR85##      50.9250.56 3.964.24 10.2510.41 8.698.78 13.9714.12 --      22 "     ##STR86##      5      ##STR87##      52.9353.08 4.254.46 10.089.78 8.459.25 13.5513.26 --      23 "     ##STR88##      6      ##STR89##      47.5647.94 3.633.48 10.9811.18 9.239.44 15.0115.17 --      24 "     ##STR90##      6 133-135 55.0354.86 3.183.45 9.319.60 8.398.10 12.8513.02 --  25 "     NHNHCH.sub.2 COOC.sub.2 H.sub.5 7 99-100 47.63 3.14 9.50 8.05 13.04 --        47.06 3.48 9.68 8.17 13.14      26 "     ##STR91##      8 70-71 41.3240.85 3.573.63 8.338.40 7.337.09 11.2611.40 6.706.41  27 "      ##STR92##      9 176-177 44.6244.75 2.332.41 11.2111.18 9.499.44 15.2315.17 --  28 "      ##STR93##      10 153-154 46.6546.22 2.892.85 10.9210.78 9.229.10 14.3914.62 --  29 "      ##STR94##      11 148-149 47.9847.59 3.123.24 9.9210.40 8.518.78 14.2114.12 --  30      ##STR95##      ##STR96##      11 181-183 48.9748.88 3.823.62 10.0710.06 8.718.49 13.4313.65 --  31 "      ##STR97##      11 188-190 50.2250.06 4.063.97 9.699.73 8.598.21 13.5213.20 --  32 "      ##STR98##      11 103-105 53.2153.22 4.854.89 8.778.87 7.737.48 11.9912.03 --  33 "      ##STR99##      10 170-171 49.9849.11 3.133.15 9.2410.11 8.748.53 13.5013.71 --  34 "      ##STR100##      11 72-73 54.0153.16 2.612.90 8.929.30 7.817.85 11.7712.62 --  35 "      ##STR101##      11 178-179 46.3546.13 2.202.13 7.888.07 20.4720.43  10.7610.95 --  36 "      ##STR102##      11 145-146 54.3854.14 3.193.25 9.059.02 7.777.61 12.4012.24 --  37 "      ##STR103##      11 188-188.5 42.6442.47 2.342.38 9.839.91 17.1416.72 14.0313.44 --  38     "      ##STR104##      11 173-174 36.9436.53 1.751.64 8.648.52 27.6628.76 11.6411.56 --  39 "      ##STR105##      11 151-152 44.2643.85 2.332.76 9.329.59 16.3416.18 13.1813.00 --  40 "      ##STR106##      11 164-165 46.6847.17 2.592.45  7.557.86 19.0019.89 9.9810.66 --  41 "      ##STR107##      12 152-153 46.6045.81 2.732.49 9.279.43 7.827.95 12.4912.79 --  42 "      ##STR108##      12 165-166 47.0247.02 2.592.85 8.789.14 7.507.71 13.1412.40 --  43 "      ##STR109##      12 123-124 46.6346.81 3.243.27 10.319.10 8.057.68 12.5712.34 --  44 "      ##STR110##      12  117-118 47.9047.96 3.113.60 8.558.83 7.547.45 12.0311.98 --  45 "      ##STR111##      12 96-97 48.81 49.04 3.363.91 8.178.58 7.937.24 11.2311.64 --  46 "      ##STR112##      12 121-123 48.1347.96 3.173.60 8.408.83 7.407.45 11.8111.98 --  47 "      ##STR113##      11 210-212 46.2846.00 2.182.65 9.9610.06 9.268.49 13.6013.64 --  48 "     NHNHSO.sub.2 CH.sub.3 13 206-207 40.15 2.50 9.56 8.33 13.54 7.57     39.49 2.60 9.87 8.32 13.39 7.53      49 "     ##STR114##      13 146-147 47.8947.86 2.913.01 8.018.37 7.447.06 11.3011.36 6.736.39     50 "      ##STR115##      13 173-174 decomp. 43.35 42.82 2.182.27 10.2310.51 6.566.65 10.8810.69     5.736.01  51 " NHNHSO.sub.2 NHCH.sub.3 13 182 decomp. 38.40 2.16 12.41     8.14 12.75 7.54      38.14 2.74 12.71 8.04 12.93 7.24      52 "     ##STR116##      14  130-131 44.3744.40 2.512.73 10.3110.36 8.638.74 13.8314.05 --  53 "      ##STR117##      14 118-119 42.7242.92 2.893.12 9.9210.01 8.368.45 13.5913.58 --  54 "      ##STR118##      14 99-101 48.2448.50 3.673.39 9.239.43 8.177.95 12.5912.79 --  55 "      ##STR119##      14 115-116 46.2247.07 3.433.49 9.489.69 8.588.17 13.3313.14 --  56 "      ##STR120##      14 118-110 48.2648.50 3.323.39 9.049.43 7.987.95 12.5512.79 --  57 "      ##STR121##      14 133-134.5 51.6651.35 2.562.80 8.868.98 7.587.58 11.9712.19 --  58 "      ##STR122##      15 83-84 50.6050.81 4.924.86 8.008.08 6.906.82 10.8010.96 6.176.17  59     "      ##STR123##      16 167-168 44.5944.51 2.912.99 13.8913.84 8.708.76 14.0414.08 --  60 "      ##STR124##      16 184-185 45.8245.89 3.323.37  13.2713.38 8.388.47 13.5013.61 --  61 "      ##STR125##      16 183.5-184.5 47.7647.18 3.503.73 12.9112.95 8.128.19 12.9713.17 --     62 "      ##STR126##      16 195-195.5 47.3347.18 3.543.73 13.0112.95 8.768.19 13.0113.17 --  63     "      ##STR127##      16 144-145 50.7050.58 4.354.67 11.6511.80 7.417.47 11.8312.00 --  64 "      ##STR128##      16 186.5-188 44.3944.84 1.832.26 10.3310.46 20.0719.86 10.4810.64 --     65 "      ##STR129##      17 180.5-183  41.1641.34 2.492.48 13.3313.77 8.628.72 13.7514.01     7.987.88      66 "     ##STR130##      18 160-161.5 45.1842.81 3.372.88 12.9313.32 8.848.43 13.3213.55     7.367.62      67 "     ##STR131##      18 180-181 44.2144.19 2.683.24 12.9012.88 7.918.15 13.0513.10 7.767.37     68 "      ##STR132##      18 197-198 46.7946.70 4.123.92 12.1012.10 8.277.66 12.1912.31 7.146.93     69 "      ##STR133##      18 162-163 47.5045.69 3.243.16 12.5912.54 8.007.94 12.5012.76 7.077.18     70 "      ##STR134##      18 151-152 49.6849.13 4.054.12 11.7311.46 7.687.25 11.3911.66 6.926.56     71 "      ##STR135##      19 149-150 41.2841.11 1.511.42 8.468.46 20.6721.40 12.5611.47 --  72 "      ##STR136##      19 157-159 51.8852.13 2.553.54 8.688.68 7.827.33 11.5811.78 --  73 "      ##STR137##      20 207-208 54.4554.38 2.782.82 9.149.06 8.347.64 11.3912.29 --  74 "      ##STR138##      19 168-171 47.4047.51 2.562.58 9.889.78 8.288.25 13.0513.26 --  75 "      ##STR139##      19 175-176 49.0848.72 2.892.95 9.449.47 8.467.99 12.9512.84 --  76 "      ##STR140##      21 96-97 46.4946.48 3.003.06 10.7911.62 9.269.80 15.2815.76 --  77 "      ##STR141##      6      ##STR142##      48.0647.94 3.573.49 11.1011.17 10.159.44 15.0015.17 --      78 "     ##STR143##      7 73-74 47.2447.07 3.383.49 9.189.69 8.378.17 13.0113.14 --  79 "      ##STR144##      10 149-150 47.5447.59 3.083.24 10.3710.40 8.828.78 13.9914.12 --  80 "      ##STR145##      11 168-169 49.1248.87 3.453.63 10.1810.06 8.618.48 13.7413.64 --  81 "      ##STR146##      11 160-161 53.9354.14 3.243.25 8.579.02 7.367.61 12.0012.24 --  82 "      ##STR147##      11 134-135 43.7843.85 2.552.77 9.629.59 16.4516.18 12.8713.01 --  83 "      ##STR148##      11 111.5-112.5 36.9137.89 1.721.99 8.058.83 27.5127.96 11.2111.24 --     84 "      ##STR149##      12 96-97 49.9350.06 5.004.20 8.748.34 7.527.04 10.9711.31 --  85 "      ##STR150##      22 117-118 40.4140.96 2.932.99 9.009.56 8.988.06 12.8412.96 7.627.29     86 "      ##STR151##      22 160-161.5 36.8837.10 2.522.93 8.068.12 6.646.84 10.5511.01 11.8112.38      87 "     ##STR152##      23 124-126 38.7139.61 2.813.11 11.9212.32 7.377.79 12.3812.53 7.017.05     88 "      ##STR153##      14 72.5-73.5 46.6345.78 2.933.13 10.0210.01 8.668.45 13.3413.56 --  89     "      ##STR154##      14 103-105 46.9147.07 3.193.49 9.619.69 8.548.17 13.3513.14 --  90 "      ##STR155##      15 65-66 51.7451.72 5.215.11 8.377.87 6.686.64 10.3710.67 6.166.00  91     "      ##STR156##      16 179-180.5 45.3945.88 3.113.38 13.0313.38 8.618.46 12.78 13.61 --  92     "      ##STR157##      26 47-48 45.9045.43 3.493.61 14.5914.72 6.997.45 11.5911.98 --  93 "      ##STR158##      18      ##STR159##      45.5645.48 3.473.60 11.9212.48 8.087.90 13.0212.70 7.527.14  94 "      ##STR160##      5 87-88 48.1447.94 3.233.49 11.1511.19 9.419.44 15.0015.17 --  95 "      ##STR161##      10 124-125 49.0448.87 3.593.62 9.9510.06 9.078.49 13.7813.65 --  96 "      ##STR162##      11 165.5-167 50.7050.06 4.043.97 9.619.74 8.287.98 13.0113.20 --  97 "      ##STR163##      5      ##STR164##      48.5849.30 3.593.88 10.0410.78 10.249.10 14.4714.63 --      98 "     ##STR165##      5      ##STR166##      50.9250.56 3.864.24 10.2510.41 8.698.78 13.9714.12 --      99 "     ##STR167##      5      ##STR168##      50.0349.81 2.782.87 10.5410.90 9.489.19 14.5714.78 --      100 "     ##STR169##      5      ##STR170##      53.8753.84 3.043.09 10.129.92 8.398.67 13.6213.45 --      101 "     ##STR171##      11 178-179 60.2959.00 3.093.37 7.067.37 6.246.22 9.8610.00 --  102 "      ##STR172##      24 106-107 48.5148.07 3.073.18 8.248.85 6.867.48 11.5612.00 --  103 "      ##STR173##      25 134- 135 46.9146.81 3.473.27 9.549.09 8.497.68 12.1812.34 --  104 "      ##STR174##      26      ##STR175##      46.8046.91 3.383.50 12.0512.16 7.077.69 12.1812.37 --      105 "     ##STR176##      20      ##STR177##      43.7243.14 3.062.86 7.507.94 20.2120.12 10.4610.78 --      106 "     ##STR178##      20 167-168 58.1858.33 2.483.08 7.497.56 6.696.38 10.1310.25 --  107 "      ##STR179##      20 83-85 46.1146.74 2.221.88 6.196.05 25.5225.55 7.958.21 --  108 "      ##STR180##      25 92-94 44.2244.03 2.852.82 9.099.06 8.067.65 11.9912.29 --  109 "      ##STR181##      25      ##STR182##      45.7246.39 2.893.48 8.048.54 7.157.21 10.9211.59 --      110 "     ##STR183##      25 67-68 55.2355.16 3.072.92 6.207.15 5.516.03 9.419.70 --  111 "     NHNCHCH.sub. 3 27 153.5-156.5 48.05 2.73 11.31 10.01 14.98 --      48.20     2.97 11.24 9.49 15.25      112 "     ##STR184##      27 113.5-114.5 50.7850.82 3.753.76 10.3210.46 9.258.83 14.3014.19 --     113 " NHNCHC.sub.7 H.sub.15 (n) 27 93-94 54.99 4.97 9.34 8.20 12.60 --        55.08 5.06 9.18 7.74 12.45 114 " NHNCHCHCH.sub.2 27 167-167.5 49.83     2.80 10.76 9.47 14.97 --      49.82 2.88 10.89 9.19 14.78 115 " NHNCHCHCH     CH.sub.3 27 177.5-179 50.97 3.12 10.30 9.01 14.41 --      51.07 3.28     10.51 8.87 14.26      116 "     ##STR185##      27 202-203 55.2055.12 3.133.01 9.549.64 8.968.14 12.9913.08 --  117 "      ##STR186##      27 190.5-197 43.3144.14 2.082.47 10.2710.29 17.2217.37 13.6913.97 --     118 " NHNCHOCH.sub.3 4 131-132 45.42 2.58 10.47 9.37 14.40 --      46.23     2.85 10.78 9.10 14.63 119 " NHNCHOC.sub.2 H.sub.5 4 119-120 47.94 3.15     10.39 8.87 13.94 --      47.60 3.24 10.41 8.78 14.12 120 " NHNCHCH.sub.2     Cl 27 115-117.5 43.31 2.08 10.27 17.22 13.69 --      44.14 2.47 10.29     17.37 13.97      121 "     ##STR187##      27 161-164 48.5648.87 3.133.62 10.4910.06 9.138.49 13.3913.64 --  122 "      ##STR188##      27 207-208 57.1557.21 3.013.27 9.269.10 8.077.68 12.5312.34 --  123 "      ##STR189##      28 108-113 44.3044.13 2.272.47 9.9410.29 18.3017.37 13.7713.96 --  124     "      ##STR190##      29 134-135 49.2349.56 3.263.38 10.7710.84 9.509.14 14.0014.70 --  125 "      ##STR191##      27 85-86 51.2950.82 3.733.76 10.5810.46 8.928.83 13.8814.19 --  126 "      ##STR192##      27 62.5-63 57.2457.65 5.835.85 8.268.40 7.097.09 11.2111.40 --  127 "      ##STR193##      27 139-140 51.4151.07 3.143.28 10.3610.51 8.378.87 14.0114.26 --  128 "      ##STR194##      27 178-180 56.4456.07 3.203.36 9.839.34 7.887.88 12.7912.67 --  129 "      ##STR195##      4 94-116 49.0748.87 3.433.62 10.1410.06 8.788.49 13.4013.64 --  130 "      ##STR196##      27 177-178 45.6945.51 2.792.87 9.889.95 16.8616.80 13.2713.50 --  131 "      ##STR197##      27 98-99 42.1642.08 2.102.43 9.189.20 23.0123.29 12.6312.48 --  132 "      ##STR198##      27      ##STR199##       49.3648.99 3.683.38 10.0910.08 8.368.51 13.4313.68 --      133 "     ##STR200##      27 171-172 48.5548.49 3.513.39 9.279.43 8.017.95 12.6812.79 --  134 "      ##STR201##      27 125-126 49.5049.63 3.403.73 9.149.14 7.347.71 12.6812.40 --  135 "      ##STR202##      27 83-84.5 51.9551.99 4.024.12 10.0110.11 8.848.53 13.9913.71 --  136 "      ##STR203##      4 87-96 50.2650.07 3.763.97 9.669.73 8.458.21 12.9913.20 --  137 "      ##STR204##      27 119-124 55.7955.64 3.262.97 11.7911.80 7.827.46 11.8812.00 --  138 "      ##STR205##      27 77.5-79 42.5842.08 2.392.43 9.179.20 23.3723.29 12.2212.48 --  139 "      ##STR206##      27 172-173 60.5861.00 3.353.35 7.948.21 7.016.93 11.0011.14 --  140 "      ##STR207##      30 121-124 41.8042.52 2.502.46 8.949.30 8.647.84 12.5512.61 13.2814.19     141 "      ##STR208##      27 150-151 53.3453.34 4.094.01 9.759.82  8.858.29 13.5113.32 --  142 "      ##STR209##      29      ##STR210##      50.3850.81 3.523.77 10.2310.46 9.068.86 14.0014.19 --      143     ##STR211##      ##STR212##      3 153-155 52.6752.26 3.753.76 12.5013.06 11.3211.02 -- --      144     ##STR213##      " 3 115-118 59.5159.79 4.755.02 13.6913.95 -- -- --      145     ##STR214##      " 3 179-180 47.6547.21 3.103.11 11.5411.80 19.5719.91 -- --  146      ##STR215##      " 3 106-107 54.2453.65 3.844.20 11.5712.51 10.7310.56 -- --  147      ##STR216##      " 10 192-193 44.9844.94 2.682.69 10.8711.23 19.2918.95 5.005.08 --  148      ##STR217##      NHNCHOCH.sub.3 4 114-115 52.6952.26 3.373.76 12.9413.06 11.2911.02 --     --      149     ##STR218##      ##STR219##      11 154-155 47.0646.65 3.343.39 11.2010.88 18.6318.36 -- --  150 "      ##STR220##      6 72.5-74.5 49.2849.13 3.963.82 12.0412.28 19.9820.72 -- --  151 "      ##STR221##      21 111-112.5 47.4347.57 3.063.38 12.1512.81 21.3021.61 -- --  152 "      ##STR222##      10 140-142 48.5748.66 3.423.54 10.8311.35 19.4819.15 -- --  153 "      ##STR223##      11 152.5-154.5 50.2450.01 3.843.94 10.3610.94 18.6218.45 -- --  154      ##STR224##      ##STR225##      19 90-92 49.2449.77 3.513.20 10.3410.25 17.9217.29 -- --      155     ##STR226##      ##STR227##      11 112-114 46.2145.78 3.083.12 9.7310.01 9.318.45 13.3913.58 --  156 "      ##STR228##      11      ##STR229##      50.0850.82 3.723.26 7.216.97 8.548.83 14.7714.19 --      157 "     ##STR230##      12 127-128 48.8249.04 3.263.91 7.648.58 7.557.24 11.7011.64 --  158 "      ##STR231##      19 147-148 48.5147.73 2.632.16 8.949.82 8.128.29 13.2413.33 --  159 "      ##STR232##      19 167-168 50.6249.84 3.593.30 9.499.18 8.347.75 12.6912.45 --  160 "      ##STR233##      11 169-170 45.8345.60 2.302.93 9.369.38 7.457.92 12.7412.73 --  161 "      ##STR234##      24      ##STR235##      47.0147.29 3.213.03 10.029.73 8.318.21 13.5113.20 --      162 "     ##STR236##      11 101-103 47.3447.96 3.513.60 8.568.83 7.717.45 11.7011.98 --  163 "      ##STR237##      10 143-145 50.1950.06 3.913.97 9.639.74 8.348.21 12.9913.20 --  164 "      ##STR238##      11 132-135 51.6251.18 4.374.30 9.449.43 8.007.95 12.5712.79 --  165 "      ##STR239##      12 126-128 47.0246.81 3.313.27 9.089.10 7.827.68 11.9812.34 --  166 "      ##STR240##      12 92-93 47.9147.96 3.663.60 8.728.83 7.447.45 11.7811.98 --  167 "      ##STR241##      12 90-91 49.1349.04 3.923.91 8.428.58 7.337.24 11.50 11.64 --  168 "      ##STR242##      28 101-102 47.9948.01 3.933.58 9.259.33 16.3615.75 12.8512.66 --  169 "      ##STR243##      11      ##STR244##      44.1444.30 2.422.55 9.969.68 7.708.17 13.2913.14 --      170 "     ##STR245##      31 201-202 48.1648.71 3.242.95 9.969.47 7.747.99 12.9312.84 --  171 "      ##STR246##      31 266-268 (decomp.) 44.3944.87 2.412.15 11.6511.21 9.189.46 15.5515.21     --      172 "     ##STR247##      31 233-234 44.6944.95 2.472.24 11.2211.65 9.369.83 16.0315.80 --  173 "      ##STR248##      32 101.5-102.5 47.5947.32 3.303.01 10.4110.36 8.789.48 14.1214.11 --     174 "      ##STR249##      32      ##STR250##      48.8748.52 3.633.66 10.0610.11 8.488.72 13.6413.57 -- 175      ##STR251##      ##STR252##      12 77-78 50.3450.06 3.984.20 8.438.34 7.227.04 11.0611.31 --  176 "      ##STR253##      14 90-92 48.7848.27 3.733.83 9.469.38 8.197.92 12.5612.73 --  177 "      ##STR254##      12 (1720) 51.2351.01 4.124.47 8.508.11 6.816.84 11.1911.00 --  178      ##STR255##      ##STR256##      10 160-162 46.7746.40 3.453.11 10.3810.82 17.9818.26 4.674.89 --  179 "      ##STR257##      21 116-118 45.5645.10 2.622.91 12.4412.13 20.3120.48 5.085.49 --  180 "      ##STR258##      21 139-140 46.9346.68 3.033.36 11.7411.67 19.9519.69 5.065.27 --  181 "      ##STR259##      10 160-161 49.0649.05 3.763.88 10.0910.10 17.2917.04 4.594.57 --  182 "      ##STR260##      11 168-169 50.5650.24 3.974.22 9.849.77 16.3516.48 4.364.42 --  183 "      ##STR261##      12 (1740) 51.3951.17 4.374.69 7.798.14 13.5313.73 3.583.68 --  184 "      ##STR262##      32 142.5-143.5 47.5247.77 3.403.51 10.6010.45 18.0117.63 4.704.72 --     185 "      ##STR263##      10 161-162 48.2847.78 3.013.50 10.6610.45 17.7617.63 4.724.72 --  186 "      ##STR264##      11 184.5-185.5 49.6149.05 3.443.87 10.2710.09 17.0717.03 4.514.56 --     187 "      ##STR265##      12      ##STR266##      50.0050.21 4.384.41 7.968.36 13.8714.11 3.473.78 --      188     ##STR267##      ##STR268##      21 154-155 44.1744.64 3.033.21 10.7711.17 28.6028.24 -- --  189 "      ##STR269##      21 143-146 43.2543.06 2.992.78 11.5511.60 29.5229.33 -- --  190 "      ##STR270##      10 158-160 44.3544.52 2.752.99 10.3010.39 26.0226.29 -- --  191 "      ##STR271##      10 185-186 47.2647.18 3.633.73 9.919.71 23.9524.58 -- --   192 "      ##STR272##      12 (1730) 49.4149.59 4.724.54 7.837.89 19.9719.96 -- --      193 "     ##STR273##      32 153-155 45.9845.90 3.203.37 10.1110.04 25.7725.41 -- --  194 "      ##STR274##      12 120-121 47.9947.59 4.143.99 8.458.33 21.2621.07 -- --  195 "      ##STR275##      12      ##STR276##      49.4248.61 4.274.26 7.728.10 19.5920.50 --  --      196 "     ##STR277##      10 184-185 45.6245.90 2.813.37 9.8210.03 25.6125.40 -- --  197 "      ##STR278##      12 1730 48.4847.59 3.703.99 7.498.32 20.1921.07 -- --      198     ##STR279##      NHNHCOCH.sub.3 10 150-151 51.0350.70 3.723.40 11.5611.82 -- 16.1616.04     --  199 " NHNHCOOC.sub.2 H.sub.5 14 99.5-100 50.14 3.58 11.08 -- 14.35     --      49.87 3.66 10.91  14.79 200 " NHNHCOCH.sub.2 Cl 11 171-172 45.89     3.17 10.42 9.51 14.54 --      46.22 2.84 10.78 9.09 14.62  201 "      ##STR280##      29 120-120.5 54.2654.39 4.233.99 11.3511.89 -- 16.0116.13 --  202 "      ##STR281##      19 166-167 52.2151.65 3.303.06 10.0210.63 -- 13.9414.42 --  203 "      ##STR282##      10 159.5-160.5 51.7852.03 4.153.82 11.3811.38 -- 15.1115.43 --  204 "      ##STR283##      32 (3350, 1680) 54.0753.26 4.164.21 11.2010.96 -- 15.1714.87 --  205 "      ##STR284##      31 249 decomp. 50.2549.42 3.122.66 11.8912.35 --  16.1216.75--  206 "     NHNHCOCH.sub.2 CH.sub.2 COOH 12 173.5-174.5 51.38 3.87 10.61 -- 14.29 --          51.39 3.55 10.57  14.35 207 " NHNHCOCH.sub.2 CH.sub.2 COOC.sub.2     H.sub.5 12 97-98 51.39 4.12 9.45 -- 13.10 --      51.70 4.11 9.52  12.91      208 "     ##STR285##      12 73-74 52.1252.75 4.594.43 9.049.23 -- 12.4312.52 --

When the compounds of the present invention are used as herbicide, theamount of the agent used is 2-50 g, preferably 5-20 g, per are for paddyfield, and 5-50 g, preferably 5-20 g for dry field crops, although theamount is affected by soil to a certain extent in the case of the soiltreatment prior to occurrence of weeds. As for the treating method,pre-plant soil incorporation, treatment of soil, treatment of filledwater, treatment of stems and leaves as well as soil, etc. are possible,but the treating method is not limited to these treatments.

In the practical use of the compounds of the present invention, they canbe used in the form of such formulations as dust, granule, wettablepowder, emulsion, etc., but the using manner is not limited to theseformulations.

The compounds of the present invention can be applied directly orindirectly to plants to be controlled, as a herbicidal compositioncontaining a generally employed carrier or as a component informulations.

The generally employed carrier referred to means any of substances whichcan be employed for dissolving, dispersing or diffusing herbicidalcompounds without harming their effectiveness and which themselves haveno harmful function upon soil, facilities, equipments employed andcrops. For example, minerals such as bentonite, clay, montmorillonite,etc., natural substances such as cellulose, thawdust, starch, etc.,resins such as polyvinyl chloride, etc. and organic solvents such asbenzene, acetone, alcohols, esters, e.g. ethyl acetate, are mentioned.

As for the surfactant employed for the purpose of emulsification,dispersion, etc., any of nonionic, anionic, cationic and amphotericsurfactants can be employed. For example, polyethylene glycol, sorbitanoleic acid monoester, sodium dodecylbenzenesulfonate,lauryltrimethylammonium chloride, stearyldimethylbetaine, etc. arementioned.

The content of the compounds expressed by the above-mentioned generalformula I, in the herbicides of the present invention is preferred to be2-10% for granules, 40-80% for wettable powder, 10-50% for emulsion and1-5% for dusts.

The formulation examples of the compounds of the present invention areshown below, but the present invention is not limited thereto.

In the formulation examples, the active ingredient compounds of thegeneral formula I are expressed by the compound No. in Table 2, and"part" refers to "part by weight".

FORMULATION EXAMPLE 1

A compound (6 parts, compound No. 78), bentonite (70 parts) talc (21parts), sodium dodecylbenzenesulfonate (2 parts) and sodiumligninsulfonate (one part) are mixed together, and a proper amount ofwater is added. After kneading, granulation is carried out in a usualmanner by means of an extruding granulator to obtain 100 parts ofgranules.

FORMULATION EXAMPLE 2

A compound (50 parts, compound No. 28), diatomaceous earth (40 parts)and sodium dodecylbenzenesulfonate (10 parts) are mixed and milled toobtain 100 parts of a wettable powder.

FORMULATION EXAMPLE 3

A compound (10 parts, compound No. 75), Solpol 800A (an emulsifier madeby Toho Kagaku Co., Japan) (10 parts) and benzene (80 parts) are mixedtogether to obtain 100 parts of an emulsion.

FORMULATION EXAMPLE 4

A compound (60 parts, compound No. 44), talc (30 parts), sodiumlaurylphosphate (7 parts) and sodium alkylnaphthalenesulfonate (3 parts)are mixed together to obtain 100 parts of a wettable powder.

FORMULATION EXAMPLE 5

A compound (5 parts, compound No. 79), bentonite (73 parts), talc (20parts), polyoxyethylene glycol monolaurate (one part) and sodiumnaphthalenesulfonate (one part) are mixed together, and a proper amountof water is then added. After kneading, granulation is carried out in ausual manner by means of an extruding granulator to obtain 100 parts ofgranules.

FORMULATION EXAMPLE 6

A compound (3 parts, compound No. 121) and clay (97 parts) aremill-mixed to obtain 100 parts of dust.

When the compounds of the present invention are used as a herbicide, itis, of course, possible to use them in admixture with one kind or moreof other herbicides, pesticides such as insecticides, germicides, plantgrowth regulators, etc., soil conditioners or fertilizable substances,and it is also possible to formulate them in admixture with theforegoing materials. Further, in some cases, a synergistic effect can beexpected.

For example, representative examples of the herbicides employed at thesame time with the herbicides of the present invention include thefollowing compounds, but they are not limited to these compounds:

Auxin herbicides

2,4-dichlorophenoxyacetic acid (including its esters and salts),

2-methyl-4-chlorophenoxyacetic acid (including its esters and salts),

4-(2,4-dichlorophenoxy)butyric acid (including its esters and salts),

3-amino-2,5-dichlorobenzoic acid,

4-chloro-2-oxobenzothiazolin-3-ylacetic acid,

Triazine herbicides

3-chloro-4,6-bis(ethylamino)-1,3,5-triazine,

2,4-bis(ethylamino)-6-methylthio-1,3,5-triazine,

2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine,

2-ethylamino-4-isopropylamino-6-methylthio-1,3,5-triazine,

2-chloro-4-diethylamino-6-ethylamino-1,3,5-triazine,

Urea herbicides

3-(3,4-dichlorophenyl)-1,1-diethylurea,

3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea,

1,1-dimethyl-3-(3-trifluoromethylphenyl)urea,

1-(2-methylcyclohexyl)-3-phenylurea,

3-(4-chlorophenyl)-1-methoxy-1-methylurea,

3-[(4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea,

3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea,

Acid anilide herbicides

3',4'-dichloropropionanilide,

2-methyl-4-chlorophenoxyaceto-O-chloroanilide,

α-chloro-N-isopropylacetanilide,

5-chloro-4-methyl-2-propionanilido-1,3-thiazole,

2-chloro-(2',6'-dinitroanilino)-N-methylpropionate,

2-chloro-2',6'-diethyl-N-(butoxymethyl)acetanilide,

2-chloro-2',6'-diethyl-N-(propoxyethyl)acetanilide,

2-chloro-N-isopropylacetanilide,

Hydroxybenzonitrile herbicides

4-hydroxy-3,5-diiodobenzonitrile,

3,5-dibromo-4-hydroxybenzonitrile,

4-hydroxy-3,5-diiodobenzonitrile octanoate,

Uracil herbicides

3-tert-butyl-5-chloro-6-methyluracil,

5-bromo-3-sec-butyl-6-methyluracil,

3-cyclohexyl-5,6-trimethyleneuracil,

Diphenyl ether herbicides

2,4-dichloro-4'-nitrodiphenyl ether,

2,4,6-trichloro-4'-nitrodiphenyl ether,

2,4-dichloro-3'-methoxy-4'-nitrodiphenyl ether,

2-nitro-4-trifluoromethyl-4'-nitrodiphenyl ether,

2-chloro-4-trifluoromethyl-4'-nitrodiphenyl ether,

2-chloro-4-trifluoromethyl-3'-methoxycarbonyl-4'-nitrodiphenyl ether,

methyl(±)-2-[4-(2,4-dichlorophenoxy)phenoxy]propionate,

Carbamic acid herbicides

isopropyl-N-phenylcarbamate,

isopropyl-N-(3-chlorophenyl)carbamate,

methyl-N-(3,4-dichlorophenyl)carbamate,

S-ethyldipropylthiocarbamate,

S-p-chlorobenzyldiethylthiocarbamate,

methyl-N-(4-amino-benzenesulfonyl)carbamate,

ethyl-N,N-di-n-propylthiocarbamate,

4-chlorobenzyl-N,N-diethylthiocarbamate,

ethyl-N,N-hexamethylenethiocarbamate,

Aniline herbicides

2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline,

N-butyl-N-ethyl-2,6-dinitro-4-trifluoromethylaniline,

3,4-dimethyl-2,6-dinitro-N-1-ethylpropylaniline,

Pyridinium salt herbicides

1,1'-dimethyl-4,4'-bispyridinium dichloride,

9,10-dihydroxy-8a,10a-diazoniaphenanthrone dibromide,

Other herbicides

N,N-bis(phosphonomethyl)glycine,

α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine,

S-(2-methyl-1-pyperidylcarbonylmethyl)-o,o-dipropylphosphorodithioate,

4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5-one,

o-ethyl-o-(2-nitro-5-methylphenyl)-N-sec-butylphosphoroamidothioate,

N-(o,o-dipropyldithiophosphorylacetyl)-2-methylpyperidine,

2,4-diamino-5-methylthio-6-chloropyrimidine.

The herbicidal activity of the compounds of the present invention willbe illustrated by way of Test examples.

TEST EXAMPLE 1

Test for controlling weeds for dry field crops according to the soiltreatment prior to germination.

An air-dried soil of dry field (passed through a 14 mesh sieve) (10 Kg)was put in a pot made of resin (a/1000), and a compound fertilizer (N,P₂ O₅ and K₂ O, each 1 g) was applied to the whole layer of the soil,followed by making the water content of the soil 60% of the maximumwater-holding capacity. The soil was seeded with a fixed amount of seedsof a crop to be tested, or weeds, and covered with soil. A liquidobtained by diluting a fixed amount of an emulsion prepared from acompound to be tested, according to Formulation example 3, with water inan amount corresponding to 10 l per are, was sprayed onto the soil bymeans of a slight pressure sprayer.

The resulting pot was placed in a greenhouse and water administrationwas always carried out to grow the plant. Thirty days after the spray ofthe agent, the occurrence or growth condition of weeds and crops wasinvestigated to obtain the results shown in Table 3.

In this Table, the phytotoxicity extent upon crops and the herbicidaleffect upon weeds, were expressed according to the evaluation standardsmentioned below, in comparison of the occurrence or growth condition ofweeds or crops, with the air-dried weight of weeds or crops in untreatedsection.

The compounds to be tested were shown by the compound No. of Table 2(this applies to the Test examples mentioned below) Among the compoundsto be tested, of Table 3, compounds Nos. 11, 13, 15, 16, 24, 177, 186and 191 could completely control the following weeds in an amount ofagent used, of 10 g/a, and others could control them in an amount ofagent used, of 5 g/a:

Foxtail, Bluegrass, Foxtailgrass, Johnsongrass, Bermudagrass,Quackgrass, Smartweed, Velvetleaf, Morningglory, Hertleaf cocklebur,Rumex japonicus, Wild mustard, Shepherdspurse, etc.

Evaluation standards:

    ______________________________________                                        0:      Percentage of existence of weeds or                                                                 76-100%                                                 crops indicated by the air-dried                                              weight ratio relative to weeds or                                             crops in untreated section                                            1:      Percentage of existence of weeds or                                                                51-75%                                                   crops indicated by the air-dried                                              weight ratio relative to weeds or                                             crops in untreated section                                            2:      Percentage of existence of weeds or                                                                36-50%                                                   crops indicated by the air-dried                                              weight ratio relative to weeds or                                             crops in untreated section                                            3:      Percentage of existence of weeds or                                                                11-35%                                                   crops indicated by the air-dried                                              weight ratio relative to weeds or                                             crops in untreated section                                            4:      Percentage of existence of weeds or                                                                 6-10%                                                   crops indicated by the air-dried                                              weight ratio relative to weeds or                                             crops in untreated section                                            5:      Percentage of existence of weeds or                                                                 0-5%                                                    crops indicated by the air-dried                                              weight ratio relative to weeds or                                             crops in untreated section                                            ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        Amount                                                                        of active   Weeds                                                             Tested ingre-                 Red-                                            com-   dient            Barn- root Lambs-                                                                              Crops                                pound  used,    Crab-   yard- pig- quar- Soy- Cot-                            No.    g/a      grass   grass weed ters  bean ton                             ______________________________________                                        8      5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               11     5        5       4     4    5     0    0                                      10       5       5     5    5     0    0                               13     5        5       5     4    5     0    0                                      10       5       5     5    5     0    0                               15     5        5       4     4    4     0    0                                      10       5       5     5    5     0    0                               16     5        5       5     4    4     0    0                                      10       5       5     5    5     0    0                               19     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               20     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               22     5        5       5     4    4     0    0                                      10       5       5     5    5     0    0                               23     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               24     5        4       4     5    5     0    0                                      10       5       5     5    5     0    0                               27     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               28     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               29     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               30     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               32     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               36     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               37     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               39     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               42     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               43     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               44     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               45     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               47     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               51     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               52     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               53     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               54     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               55     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               56     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               57     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               71     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               72     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               73     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               74     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               75     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               76     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               77     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               78     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               79     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               84     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               87     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               94     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               95     5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               108    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               109    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               110    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               118    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               119    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               120    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               121    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               124    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               125    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               129    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               131    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               134    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               135    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               143    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               144    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               145    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               146    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               148    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               149    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               150    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               155    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               156    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               157    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               158    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               159    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               160    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               161    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               165    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               166    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               167    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               168    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               169    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               170    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               171    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               172    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               177    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               183    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               186    5        5       5     5    4     0    0                                      10       5       5     5    5     0    0                               189    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               191    5        5       5     4    4     0    0                                      10       5       5     5    5     0    0                               193    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               196    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               198    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               199    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               200    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               202    5        5       5     5    5     0    0                                      10       5       5     5    5     0    0                               205    5        5       5     5    4     0    0                                      10       5       5     5    5     0    0                               Com-   20       5       4     4    4     0    0                               merical                                                                              40       5       5     5    5     0    0                               product                                                                       NIP *                                                                         Un-    Number   43      38    28   19    5    5                               treated                                                                              of plants.                                                             section                                                                              Air-dried                                                                              2.8     4.1   2.4  2.8   10.3 6.4                                    weight of                                                                     plants (g)                                                             ______________________________________                                          *Active ingredient: 2,4dichloro-4'-nitrodiphenyl ether                  

TEST EXAMPLE 2

Herbicidal test for treating stems and leaves of dry field crops.

An air-dried soil of dry field (passed through a 14 mesh sieve) (450 g)was placed in a pot made of a resin (a/10000), and a compound fertilizer(N, P₂ O₅ and K₂ O, each 100 mg) was applied to the whole layer of thesoil, followed by adjusting the water content of the soil to 60% of themaximum water-holding capacity. The soil was seeded with a fixed amountof seeds of a plant to be tested, and uniformly covered with soil. Theresulting pot was placed in a glass-covered greenhouse, and when theplant to be tested grew till the period in 2-3 leaves, treatment ofstems and leaves was carried out employing a wettable powder preparedaccording to the above-mentioned Formulation example 4, so as to containthe agent to be tested, in an amount of 1000, 2000 or 5000 ppm in termsof active ingredient.

Thirty days after the treatment, the growth condition of the plant to betested was investigated to obtain the results shown in Table 4. Inaddition, in this Table, the designated sections of the growth conditionof the crops and weeds are the same as those of Table 3.

Among the compounds shown in Table 4, compounds Nos. 5, 9, 26, 61, 62,63, 70, 175, 179, 186, 190 and 197 could completely control thefollowing weeds, in an amount of agent used, of 5 g/a, and othercompounds could control them in an amount of agent used, of 2 g/a:

Foxtail, Bluegrass, Foxtailgrass, Johnsongrass, Bermudagrass,Quackgrass, Smartweed, Velvetleaf, Morningglory, Hertleaf cocklebur,Rumex japonicus, Wild mustard, Shepherdspurse, etc.

                  TABLE 4                                                         ______________________________________                                        Amount      Weeds                                                             Tested                                                                              of active               Red-                                            com-  ingredient        Barn- root Lambs-                                                                              Crops                                pound used,     Crab-   yard- pig- quar- Soy- Cot-                            No.   g/a       grass   grass weed ters  bean ton                             ______________________________________                                        5     2         5       5     4    5     0    0                                     5         5       5     5    5     0    0                               9     2         5       5     4    5     0    0                                     5         5       5     5    5     0    0                               12    2         5       5     5    4     0    0                                     5         5       5     5    5     0    0                               15    2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               17    2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               18    2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               23    2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               26    2         5       5     4    4     0    0                                     5         5       5     5    5     0    0                               27    2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               31    2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               44    2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               45    2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               59    2         5       5     4    5     0    0                                     5         5       5     5    5     0    0                               61    2         5       5     4    5     0    0                                     5         5       5     5    5     0    0                               62    2         5       5     4    5     0    0                                     5         5       5     5    5     0    0                               63    2         5       5     4    5     0    0                                     5         5       5     5    5     0    0                               64    2         5       5     4    5     0    0                                     5         5       5     5    5     0    0                               66    2         5       5     5    4     0    0                                     5         5       5     5    5     0    0                               67    2         5       5     5    4     0    0                                     5         5       5     5    5     0    0                               69    2         5       5     5    4     0    0                                     5         5       5     5    5     0    0                               70    2         5       5     5    4     0    0                                     5         5       5     5    5     0    0                               71    2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               73    2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               74    2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               76    2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               77    2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               84    2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               94    2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               95    2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               97    2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               98    2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               99    2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               100   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               101   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               118   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               119   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               123   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               132   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               133   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               137   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               140   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               142   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               169   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               173   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               174   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               175   2         5       5     4    4     0    0                                     5         5       5     5    5     0    0                               176   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               179   2         5       4     4    4     0    0                                     5         5       5     5    5     0    0                               182   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               185   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               186   2         5       4     5    5     0    0                                     5         5       5     5    5     0    0                               187   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               188   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               190   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               192   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               194   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               195   2         5       4     5    5     0    0                                     5         5       5     5    5     0    0                               197   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               201   2         5       5     5    4     0    0                                     5         5       5     5    5     0    0                               202   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               206   2         5       5     5    4     0    0                                     5         5       5     5    5     0    0                               207   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               208   2         5       5     5    5     0    0                                     5         5       5     5    5     0    0                               Com-  10        4       4     4    4     2    2                               mercial                                                                             20        5       5     5    5     3    3                               product                                                                       NIP                                                                           Un-   Number    10      10    10   10    5    5                               treated                                                                             of plants                                                               section                                                                             Air-dried 22.5    31.8  30.9 29.3  3.3  7.1                                   weight                                                                        of plants                                                                     (g)                                                                     ______________________________________                                    

TEST EXAMPLE 3

Herbicidal test for initial period paddy field (1).

A paddy field soil wherein seeds of general weeds of paddy field werenaturally present in admixture (passed through a 14 mesh sieve) (3.3 Kg)was placed in a Wagner pot (a/5000), and a compound fertilizer (N, P₂ O₅and K₂ O, each 0.8 g) was applied to the whole layer of the soil,followed by adding a proper amount of water and stirring to form awater-filled state. The soil was seeded with seeds of weeds of paddyfield and tubers of Sagittaria trifolia and Eleocharis kuroguwai, andtwo stocks, each consisting of two young aquatic rice plants (leaf ageof young plant: 3.0), grown in advance, were transplanted to grow themin a greenhouse.

At the initial period of occurrence of weeds two days after thetransplantation of the aquatic rice plants, treatment was carried outunder the water-filled condition, employing granules prepared from afixed amount of compounds to be tested, according to the above-mentionedFormulation example 5.

One month after the treatment, the occurrence condition of weeds and theextent of phytotoxicity upon the aquatic rice plants were investigatedto obtain the results shown in Table 5. In this Table, the sectionsdesignating the occurrence condition of weeds were made 6 stages as inTest example 1, and the sections designating the extent of phytotoxicityupon aquatic rice plants were made 6 stages of "serious harm", "largeharm", "medium harm", "small harm", "slight harm" and "non-harm".

In addition, during the test period, the water-filled depth of the potwas maintained at 3 cm, by way of a water-leakage treatment of 1 cm/day.

Among the tested compounds shown in Table 5, compounds Nos. 1, 2, 4, 6,48, 93, 103, 191 and 192 could control Eleocharis kuroguwal andSagittaria trifola in an amount of agent used, of 15 g/a, and othercompounds could control them in an amount of agent used, of 7 g/a.

Evaluation standards upon phytotoxicity:

    ______________________________________                                        Serious harm:                                                                          Percentage of existence of crops                                                                   0-10%                                                    indicated by the air-dried weight                                             ratio relative to crops in                                                    untreated section                                                    Large harm:                                                                            Percentage of existence of crops                                                                  11-20%                                                    indicated by the air-dried weight                                             ratio relative to crops in                                                    untreated section                                                    Medium harm:                                                                           Percentage of existence of crops                                                                  21-50%                                                    indicated by the air-dried weight                                             ratio relative to crops in                                                    untreated section                                                    Small harm:                                                                            Percentage of existence of crops                                                                  51-80%                                                    indicated by the air-dried weight                                             ratio relative to crops in                                                    untreated section                                                    Slight harm:                                                                           Percentage of existence of crops                                                                  81-95%                                                    indicated by the air-dried weight                                             ratio relative to crops in                                                    untreated section                                                    Non-harm:                                                                              Percentage of existence of crops                                                                   96-100%                                                  indicated by the air-dried weight                                             ratio relative to crops in                                                    untreated section                                                    ______________________________________                                    

                                      TABLE 5                                     __________________________________________________________________________    Amount      Weeds                                                                   of active Small-    Narrow-                                             Tested                                                                              ingredient                                                                          Barn-                                                                             flower    leaf Annual                                                                            Crops                                      compound                                                                            used, yard-                                                                             umbrella-                                                                          Scirpus                                                                            water-                                                                             broad                                                                             Aquatic                                    No.   g/a   grass                                                                             plant                                                                              juncoides                                                                          plantain                                                                           leaf                                                                              rice                                       __________________________________________________________________________    1     5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          2     5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          3     5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          4     5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          6     5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          8     5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          18    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          23    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          28    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          34    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          35    5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          44    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          48    5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          49    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          50    5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          51    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          58    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          65    5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          76    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          77    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          78    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          79    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          80    5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          81    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          82    5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          83    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          84    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          85    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          86    5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          88    5         5    5    5    5   Non                                              10    5   5    5    5    5   "                                          89    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          90    5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          91    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          92    5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          93    5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          94    5     5   5    5    5    5   Non                                              10    5   5    5         5   "                                          95    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          96    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          97    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          98    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          99    5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          101   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          102   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          103   5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          104   5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          105   5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          106   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          107   5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          109   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          123   5     4   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          134   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          142   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          147   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          151   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          152   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          153   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          154   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          162   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          163   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          164   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          165   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          166   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          173   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          174   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          175   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          176   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          177   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          178   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          179   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          180   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          181   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          182   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          183   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          184   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          186   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          187   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          188   5     5   4    5    4    4   Non                                              10    5   5    5    5    5   "                                          189   5     5   4    4    4    5   Non                                              10    5   5    5    5    5   "                                          190   5     5   4    4    5    5   Non                                              10    5   5    5    5    5   "                                          191   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          192   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          193   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          194   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          195   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          196   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          197   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          201   5     5   5    4    5    5   Non                                              10    5   5    5    5    5   "                                          203   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          204   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          207   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          208   5     5   5    5    5    5   Non                                              10    5   5    5    5    5   "                                          Com-  20    5   5    4    4    5   Non                                        mercial                                                                             40    5   5    5    5    5   Slight                                     product                                                                       X52*                                                                          Un-   Number of                                                                           114 38   43   62   76  4                                          treated                                                                             plants                                                                              9.1 0.12 1.81 0.23 0.14                                                                              21.1                                       section                                                                             Air-dried                                                                     weight of                                                                     plants (g)                                                              __________________________________________________________________________     *Active ingredient: 2,4dichloro-3'-methoxy-4'-nitrodiphenyl ether        

TEST EXAMPLE 4

Herbicidal test for initial period paddy field (2).

A paddy field soil wherein seeds of general weeds of paddy field werenaturally present in admixture (passed through a 14 mesh sieve) (3.3 Kg)was placed in a Wagner pot (a/5000), and a compound fertilizer (N, P₂ O₅and K₂ O, each 0.8 g) was applied to the whole layer of the soil,followed by adding water and stirring to form a water-filled state. Thesoil was seeded with seeds of weeds of paddy field and tubers ofSagittaria trifolia and Eleocharis kuroguwai, and two stocks, eachconsisting of two young aquatic rice plants (leaf age of young plant:3.0), grown in advance, were transplanted to grow them in a greenhouse.

At the initial period of occurrence of weeds seven days after thetransplantation of the aquatic rice plant, treatment was carried outunder the water-filled condition, employing granules prepared from afixed amount of compounds to be tested, according to the above-mentionedFormulation example 1.

One month after the treatment, the occurrence condition of weeds and theextent of phytotoxicity upon the aquatic rice plants were investigatedto obtain the results shown in Table 6. In this Table, the sectionsdesignating the occurrence condition of weeds were made 6 stages as inTest example 1, and the sections designating the extent of phytotoxicityupon aquatic rice plants were made 6 stages of "serious harm", "largeharm", "medium harm", "small harm", "slight harm" and "non-harm". Theevaluation standards are the same as those in Test example 3.

In addition, during the test period, the water-filled depth of the potwas maintained at 3 cm, by way of a water-leakage treatment of 1 cm/day.

Among the tested compounds shown in Table 6, compounds Nos. 10, 33, 68,112, 126, 127, 128, 132, 165, 174, 176, 186, 187, 195 and 197 couldcontrol Sagittaria trifola and Eleocharis kuroguwal in an amount ofagent used, of 20 g/a, and other compounds could control them in amamount of agent used, of 15 g/a.

                                      TABLE 6                                     __________________________________________________________________________    Amount      Weeds                                                                   of active Small-    Narrow-                                             Tested                                                                              ingredient                                                                          Barn-                                                                             flower    leaf Annual                                                                            Crops                                      compound                                                                            used, yard-                                                                             umbrella-                                                                          Scirpus                                                                            water-                                                                             broad                                                                             Aquatic                                    No.   g/a   grass                                                                             plant                                                                              juncoides                                                                          plantain                                                                           leaf                                                                              rice                                       __________________________________________________________________________    10    7     4   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          14    7     4   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          20    7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          33    7     4   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          40    7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          41    7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          42    7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          43    7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          45    7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          46    7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          68    7     4   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          74    7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          75    7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          76    7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          77    7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          83    7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          87    7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          97    7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          100   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          111   7     4   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          112   7     4   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          113   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          114   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          115   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          116   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          117   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          120   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          122   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          126   7     4   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          127   7     4   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          128   7     4   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          129   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          130   7     4   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          131   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          132   7     4   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          135   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          138   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          139   7     4   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          141   7     4   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          142   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          143   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          165   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          166   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          174   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          176   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          180   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          184   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          185   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          186   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          187   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          188   7     5   5    4    5    5   Non                                              15    5   5    5    5    5   "                                          189   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          192   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          193   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          195   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          197   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          203   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          204   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          206   7     5   5    4    5    5   Non                                              15    5   5    5    5    5   "                                          207   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          208   7     5   5    5    5    5   Non                                              15    5   5    5    5    5   "                                          Com-  40    4   4    2    4    4   Slight                                     mercial                                                                             60    5   5    3    4    5   Non                                        product                                                                       Attack                                                                        Weed*                                                                         Un-   Number of                                                                           93  28   38   75   45  4                                          treated                                                                             plants                                                                              49.1                                                                              0.11 0.29 0.38 0.21                                                                              59.2                                       section                                                                             Air-dried                                                                     weight of                                                                     plants(g)                                                               __________________________________________________________________________     *Active ingredient: 3methyl-4-nitrodiphenyl ether                        

What is claimed is:
 1. A diphenyl ether compound represented by thegeneral formula I. ##STR286## wherein; A and B are each selected fromthe group consisting of a chlorine atom, a fluorine atom, --CH₃ and--CF₃ ;m and n each represent an integer 0-3 and m+n=0-3; R represents##STR287## wherein; R¹ represents hydrogen atom, --CH₃, --C₂ H₅ or --C₃H₇ (n); R² represents hydrogen atom, --CH₃ or --C₂ H₅ ; R³ represents analkoxy group having 1 to 4 carbon atoms, ##STR288## a carboxyalkylgroup, a carbalkoxy group, a carboxyalkenyl group, a carbalkoxy-alkylgroup or a carbalkoxyalkenyl group.
 2. A compound of claim 1 representedby the general formula I wherein R³ is --COOCH₃, --COOC₂ H₅, --CH₂ CH₂COOH, --CH₂ CH₂ COOCH₃, --CH₂ CH₂ COOC₂ H₅, ##STR289## --CH₂ CH₂ CH₂COOH, --CH₂ CH₂ CH₂ COOCH₃, --CH₂ CH₂ CH₂ CH₂ COOCH₃, --CH═CHCOOH,--CH═CHCOOCH₃, --OCH₃, --OC₂ H₅, ##STR290##
 3. A compound of claim 1represented by the general formula I wherein R³ is a carboxyalkyl,carboxyalkenyl, carbalkoxy, carbalkoxyalkyl or carbalkoxyalkenyl group.4. A compound of claim 1 represented by the general formula I wherein R³is a carboxyalkyl or carboxyalkenyl group.
 5. A compound of claim 4represented by the general formula I wherein R³ is --CH₂ CH₂ COOH, --CH₂CH₂ CH₂ COOH or --CH═CHCOOH.
 6. A compound of claims 1, 2, 3, 4 or 5represented by the general formula I wherein ##STR291##
 7. A compound ofclaim 6 represented by the general formula I wherein R² is a hydrogenatom.
 8. A compound of claim 1 or 6 represented by the general formula Iwherein R³ is --CH₂ CH₂ COOH.
 9. A compound of claim 1 represented bythe general formula I wherein ##STR292## and R is --NHNHCO(CH₂)₂ COOH,##STR293##
 10. A compound of claim 1 represented by the general formulaI wherein ##STR294## and R is --NHNHCOCH₂ CH₂ COOCH₃.
 11. A compound ofclaim 1 represented by the general formula I wherein ##STR295## and R is--NHNHCOCH₂ CH₂ COO(C₂ H₅).
 12. A compound of claim 1 represented by thegeneral formula I wherein ##STR296## and R is ##STR297##
 13. A compoundof claim 1 represented by the general formula I wherein ##STR298## and ris ##STR299##
 14. A compound of claim 1 represented by the generalformula I wherein ##STR300## and R is ##STR301##
 15. A compound of claim1 represented by the general formula I wherein ##STR302## and R is##STR303##
 16. A compound of claim 1 represented by the general formulaI wherein ##STR304## and R is ##STR305##
 17. A herbicidal compositioncontaining, as an active ingredient a herbicidally effective amount of adiphenyl ether compound represented by the general formula I, ##STR306##wherein A, B, m, n and R are as defined in the formula I of claim 1 andalso containing an inert herbicidal carrier.
 18. A method of controllingweeds which comprises applying a herbicidally effective amount of acompound of claim 1 pre-emergently to the soil.
 19. A method ofcontrolling weeds which comprises applying a herbicidally effectiveamount of a compound of claim 1 to the weeds as a topical treatment.